U.S. patent number 5,108,751 [Application Number 07/655,518] was granted by the patent office on 1992-04-28 for cosmetic composition comprising 2-hydroxyalkenoic acids or a mixture thereof.
This patent grant is currently assigned to Chesebrough-Pond's USA Co., Division of Conopco, Inc.. Invention is credited to Richard J. Curtis, Desmond B. Hagan, Andrew Joiner.
United States Patent |
5,108,751 |
Hagan , et al. |
April 28, 1992 |
**Please see images for:
( Certificate of Correction ) ** |
Cosmetic composition comprising 2-hydroxyalkenoic acids or a
mixture thereof
Abstract
The invention concerns 2-hydroxyalkenoic acids within a general
formula ##STR1## where R' is chosen from: a. C.sub.w H.sub.2w, b.
C.sub.y H.sub.2y-1, and c. C.sub.y H.sub.2y OZ where z is chosen
from H, R" and (CH.sub.2).sub.n OR" R" is chosen from C.sub.m
H.sub.2m+1 and (CH.sub.2).sub.n OC.sub.m H.sub.2m+1 ; w is an
integer of from 1 to 25 y is an integer of from 2 to 25 m is an
integer of from 1 to 4 n is an integer of from 1 to 6 Many
compounds within the formula are novel and are claimed as such. The
invention also provides a process for making the compounds, and
compositions for topical application to human skin, hair or nails
which contain compounds of the above formula and a cosmetically
acceptable vehicle.
Inventors: |
Hagan; Desmond B. (South
Wirral, GB3), Joiner; Andrew (Liverpool,
GB3), Curtis; Richard J. (Wirral, GB3) |
Assignee: |
Chesebrough-Pond's USA Co.,
Division of Conopco, Inc. (Greenwich, CT)
|
Family
ID: |
10670886 |
Appl.
No.: |
07/655,518 |
Filed: |
February 13, 1991 |
Foreign Application Priority Data
|
|
|
|
|
Feb 13, 1990 [GB] |
|
|
9003201 |
|
Current U.S.
Class: |
424/401; 514/873;
424/70.1; 514/784 |
Current CPC
Class: |
A61K
8/0212 (20130101); A61Q 5/00 (20130101); A61K
8/365 (20130101); C07C 59/42 (20130101); A61Q
19/00 (20130101); C07C 67/347 (20130101); C07C
67/347 (20130101); C07C 69/675 (20130101); A61Q
19/10 (20130101); A61Q 5/12 (20130101); Y10S
514/873 (20130101); A61Q 3/00 (20130101) |
Current International
Class: |
A61Q
19/10 (20060101); A61Q 5/12 (20060101); A61Q
3/00 (20060101); A61Q 19/00 (20060101); A61Q
5/00 (20060101); A61K 8/365 (20060101); A61K
8/30 (20060101); A61K 8/02 (20060101); C07C
59/42 (20060101); C07C 59/00 (20060101); C07C
67/00 (20060101); C07C 67/347 (20060101); A61K
007/00 () |
Field of
Search: |
;424/401,70,61,59,47,69
;514/943,947,873,785,784 ;260/413Q,41.9R |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Tetrahedron Letters, vol. 27, No. 37, pp. 4511-4514 (1986). .
Tetrahedron Letters, vol. 23, No. 33, pp. 3419-3420 (1982). .
Tetrahedron Letters, vol. 22, pp. 69-72 (1981). .
J. Chem. Soc. Perk, Trans. I (1984) p. 331. .
Roczniki Chemii, Ann Soc Chim. Polononum 36, 1791 (1962)..
|
Primary Examiner: Page; Thurman K.
Assistant Examiner: Colucci; D.
Attorney, Agent or Firm: Honig; Milton L.
Claims
We claim:
1. A cosmetically acceptable composition for topical application to
human skin or hair, which comprises:
i. from 0.1 to 99.9% by weight of a 2-hydroxyalkenoic acid having
the structure (20) ##STR15## where R" is selected from the group
consisting of:
a. C.sub.w H.sub.2w,
b. C.sub.y H.sub.2y-1, and
c. C.sub.y H.sub.2y OZ
where
Z is selected from the group consisting of: H, R" and
(CH.sub.2).sub.n OR"
R" is selected from the group consisting of: C.sub.m H.sub.2m+1 and
(CH.sub.2).sub.n OC.sub.m H.sub.2m+1 ;
w is an integer of from 1 to 25
y is an integer of from 2 to 25
m is an integer of from 1 to 4
n is an integer of from 1 to 6; and
ii. from 0.1 to 99.9% by weight of a cosmetically acceptable
vehicle for the acid.
2. A composition according to claim 1, in which the
2-hydroxyalkenoic acid is selected from the group consisting
of:
2-hydroxy-4 -hexenoic acid
2-Hydroxy-4-heptenoic acid
2-hydroxy-4-octenoic acid
2-Hydroxy 4-nonenoic acid
2-hydroxy-4-decenoic acid
2-Hydroxy-4-undecenoic acid
2-hydroxy-4 -dodecenoic acid
2-Hydroxy 4-tridecenoic acid
2-Hydroxy-4-tetradecenoic acid
2-Hydroxy-4-pentadecenoic acid
2-Hydroxy-4-hexadecenoic acid
2-Hydroxy-4-heptadecenoic acid
2-Hydroxy-4-octadecenoic acid
2-Hydroxy-4-nonadecenoic acid
2-Hydroxy-4-eicosenoic acid
2-Hydroxy-4-heneicosenoic acid
2-Hydroxy-4-docosenoic acid
2-Hydroxy-4-tricosenoic acid
2-Hydroxy-4-tetracosenoic acid
2-Hydroxy-4-pentacosenoic acid
2-Hydroxy-4-hexacosenoic acid
2-Hydroxy-4-heptacosenoic acid
2-Hydroxy-4-octacosenoic acid
2-Hydroxy-4-nonacosenoic acid, and
2-Hydroxy-4-triacontencoic acid.
3. A composition according to claim 1, in which the
2-hydroxyalkenoic acid is selected from the group consisting
of:
2-Hydroxy-4,7-octadienoic acid
2-Hydroxy-4,9-decadienoic acid
2-Hydroxy-4,10-undecadienoic acid
2-Hydroxy 4,11-dodecadienoic acid
2-Hydroxy-4,13-tetradecadienoic acid
2-Hydroxy-4,15-hexadecadienoic acid
2-Hydroxy-4,17-octadecadienoic acid
2-Hydroxy 4,19-eicosadienoic acid
2-Hydroxy 4,21-docosadienoic acid
2-Hydroxy-4,23-tetracosadienoic acid
2-Hydroxy-4,25-hexacosadienoic acid
2-Hydroxy-4,27-octacosadienoic acid, and
2-Hydroxy-4,29-triacontadienoic acid.
4. A composition according to claim 1, in which the
2-hydroxyalkenoic acid is selected from the group consisting
of:
2-Hydroxy-6-oxa-4-heptenoic acid
2-Hydroxy-7-oxa-4-octenoic acid
2-Hydroxy-9 oxa-4-decenoic acid
2-Hydroxy-9-oxa-4-undecenoic acid
2-Hydroxy-11-oxa-4-dodecenoic acid
2-Hydroxy-13-oxa-4-tetradecenoic acid
2-Hydroxy-13-oxa-4-pentadecenoic acid
2-Hydroxy-14-oxa-4-pentadecenoic acid
2-Hydroxy-13-oxa-14-methyl-4-pentadecenoic acid
2-Hydroxy-11,14-dioxa-4-pentadecenoic acid
2-Hydroxy-13-oxa-4-hexadecenoic acid
2-Hydroxy-14-oxa-4-hexadecenoic acid
2-Hydroxy-15-oxa-4-hexadecenoic acid
2-Hydroxy-17-oxa-4-octadecenoic acid
2-Hydroxy-14,17-dioxa-4-octadecenoic acid
2-Hydroxy-18-oxa-4-eicosenoic acid
2-Hydroxy-18-oxa-19-methyl-4-eicosenoic acid
2-Hydroxy-19-oxa-4-docosenoic acid
2-Hydroxy-18,21-dioxa-4-tricosenoic acid
2-Hydroxy-22-oxa-4-tetracosenoic acid
2-Hydroxy-25-oxa-4-hexacosenoic acid
2-Hydroxy-24-oxa-4-heptacosenoic acid
2-Hydroxy-25-oxa-4-octacosenoic acid
2-Hydroxy-23,26-dioxa-4-octacosenoic acid, and
2-Hydroxy-29-oxa-4-triacontenoic acid.
5. A composition according to claim 1, in which the
2-hydroxyalkenoic acid forms from 0.5 to 10% by weight.
6. A composition according to claim 1, which is an emulsion.
7. A composition according to claim 1, which is a lotion.
8. A composition according to claim 6 which is a cream.
Description
FIELD OF INVENTION
The invention relates to unsaturated hydroxy acids, particularly
2-hydroxyalkenoic acids, to a process for preparing these acids,
and to their use in compositions for topical application to skin,
hair and nails.
BACKGROUND AND PRIOR ART
i) Compounds per se
Very few 2-hydroxyalkenoic acids have been reported in the
literature. These are:
2-hydroxy-4-hexenoic acid, whose synthesis is described in a paper
by Mikami et al entitled "Novel silyl triflate-mediated [2,3]
Wittig sigmatropic rearrangement. The possible interpretation of an
oxygen ylide", published in Tetrahedron Lett. 1986. 27(37),
4511-14, and abstracted in Chem. Abs. (1987), 107, 77286h.
2-Hydroxy-4-heptenoic acid, whose synthesis is described in a paper
by Achmatowicz et al entitled
"Monoenic syntheses. I. On monoenophilic reactivity of ethyl
mesoxalate", published in Roczniki Chem. 36, 1791-1813 (1962), and
abstracted in Chem. Abs. (1963), 59 8610d.
2-Hydroxy-4-octenoic acid, whose synthesis is described in a paper
by Brenner et al, entitled "Some aspects of the chemistry of
1,1,1-trihaloalk-4-en-ols, the ene adducts obtained from reaction
of chloral and bromal with alkenes", published in J. Chem. Soc.,
Perkin Trans. 1 1984 (3), 331-42, and abstracted in Chem. Abs.
(1984), 101, 38095b.
2-Hydroxy-4-dodecenoic acid, whose synthesis is described in a
paper by Takeshi et al entitled "Application of [2,3] sigmatropic
rearrangements in organic synthesis. III. The [2,3] Wittig
rearrangement of 2-alkenyloxyacetic acids and its application to
the stereocontrolled synthesis of .beta.,.gamma.-unsaturated
aldehydes and conjugated dienoic acids", published in Tetrahedron
Lett. 1981, 22(1), 69-72, and abstracted in Chem. Abs. (1981), 95,
6442d.
It is apparent that other 2-hydroxyalkenoic acids have not
previously been disclosed in the literature, and an aspect of the
invention is accordingly concerned with certain new
2-hydroxyalkenoic acids, and their synthesis.
ii) Cosmetic Compositions
A soft, supple and flexible skin has a marked cosmetic appeal and
is an attribute of normal functioning epidermis. The outer layer of
the epidermis, i.e. the stratum corneum, can, however, become dry
and flaky following exposure to adverse climatic conditions, or
excessive contact with detergents or solvents which result in loss
of skin moisture, so that the skin loses its soft, supple and
flexible characteristics. Emollients such as fats, phospholipids
and sterols have in the past been used to soften dry skin, but it
is apparent that these emollients are only partially effective as a
remedy for this type of condition. Also, typical application to the
skin of classical humectants is unlikely to alleviate this problem
since they are not particularly skin substantive and are generally
rinsed from the skin during washing.
It is therefore evident that there exists a need for an effective
treatment for skin which is in a dry, flaky condition and which is
relatively inflexible.
It has been proposed in U.S. Pat. No. 4,105,782 (Yu & Van
Scott) to use amides or ammonium salts of .alpha.-hydroxyacids in
the treatment of acne or dandruff and, in the Yu & Van Scott
patents, U.S. Pat. No. 4,105,783 and U.S. Pat. No. 4,197,316, to
use such compounds in the treatment of dry skin. U.S. Pat. No.
4,234,599 (Yu & Van Scott) discloses the use of
.alpha.-hydroxyacids, and their esters or amine salts in the
treatment of keratoses.
In U.S. Pat. No. 4,363,815 (Yu & Van Scott) it is proposed to
use .alpha.-hydroxyacids or .beta.-hydroxyacids or ketoacids or
their derivatives, including inorganic salts, in a composition for
treating skin conditions.
According to GB 1 471 679 (Avon), the use of alkali metal salts of
C.sub.2 -C.sub.5 .alpha.-hydroxycarboxylic acids in moisturising
compositions is proposed.
In DE 2 110 993 (Henkel), there are disclosed alkali metal salts of
C.sub.4 -C.sub.10 .alpha.-hydroxycarboxylic acids, and the sodium
salt of .alpha.-hydroxycaprylic acid is mentioned. These salts are
incorporated in amounts from 3-30% into washing and cleaning
compositions and are said to confer improved storage stability.
As part of a programme to examine substances for their ability to
improve skin condition, isolated guinea pig footpad stratum corneum
was selected as a model for human skin, and changes in its
elasticity were measured after application of each test substance.
The amount by which extensibility of the stratum corneum was
increased was taken as a measure of the likely skin benefit that
the substance would have on human skin.
Of the many substances screened in this way, certain
2-hydroxyalkanoic acids, as described in EP-B-O 007 785 (Unilever),
were identified for their skin benefits when included in
compositions for topical application to the skin. Such benefits
include both increased elasticity of the skin, particularly the
stratum corneum, and improved appearance. However, difficulty can
be experienced when formulating certain of these 2-hydroxyalkanoic
acids in skin cosmetic formulations, due to their poor solubility
in water.
DEFINITION OF THE INVENTION COMPOUND PER SE
The invention accordingly provides 2-hydroxyalkenoic acid having
the structure (1): ##STR2## where
R is chosen from:
a. C.sub.x H.sub.2x+1,
b. C.sub.y H.sub.2y-1, and
c. C.sub.y H.sub.2y OZ;
where
Z is chosen from H, R" and (CH.sub.2).sub.n OR"
R" is chosen from C.sub.m H.sub.2m+1 and (CH.sub.2).sub.n OC.sub.m
H.sub.2m+1 ;
x is an integer of from 4 to 6, or from 8 to 25
y is an integer of from 2 to 25
m is an integer of from 1 to 4
n is an integer of from 1 to 6.
In further aspects the invention also provides a process for
preparing the unsaturated 2-hydroxyalkenoic acids, and skin, hair
and nail treatment compositions incorporating unsaturated
2-hydroxyalkenoic acids.
DISCLOSURE OF THE INVENTION
The 2-hydroxyalkenoic acid
The unsaturated 2-hydroxyalkenoic acid has the structure (1):
##STR3## where
R is chosen from:
a. C.sub.x H.sub.2x+1,
b. C.sub.y H.sub.2y-1, and
c. C.sub.y H.sub.2y OZ;
where
Z is chosen from H, R" and (CH.sub.2).sub.n OR"
R" is chosen from C.sub.m H.sub.2m+1 and (CH.sub.2).sub.n OC.sub.m
H.sub.2m+1 ;
x is an integer of from 4 to 6, or from 8 to 25
y is an integer of from 2 to 25
m is an integer of from 1 to 4
n is an integer of from 1 to 6.
The new 2-hydroxyalkenoic acids in accordance with the generic
definition given herein are exemplified by three classes of new
acids, namely:
mono-unsaturated 2-hydroxyalkenoic acids, di-unsaturated
2-hydroxyalkenoic acids, and mono-unsaturated oxa-2-hydroxyalkenoic
acids (i.e. ether acids).
Examples of the new mono-unsaturated 2-hydroxyalkenoic acids, where
R is C.sub.x H.sub.2x+1 include:
2-Hydroxy-4-nonenoic acid
2-Hydroxy-4-decenoic acid
2-Hydroxy-4-undecenoic acid
2-Hydroxy-4-tridecenoic acid
2-Hydroxy-4-tetradecenoic acid
2-Hydroxy-4-pentadecenoic acid
2-Hydroxy-4-hexadecenoic acid
2-Hydroxy-4-heptadecenoic acid
2-Hydroxy-4-octadecenoic acid
2-Hydroxy-4-nonadecenoic acid
2-Hydroxy-4-eicosenoic acid
2-Hydroxy-4-heneicosenoic acid
2-Hydroxy-4-docosenoic acid
2-Hydroxy-4-tricosenoic acid
2-Hydroxy-4-tetracosenoic acid
2-Hydroxy-4-pentacosenoic acid
2-Hydroxy-4-hexacosenoic acid
2-Hydroxy-4-heptacosenoic acid
2-Hydroxy-4-octacosenoic acid
2-Hydroxy-4-nonacosenoic acid, and
2-Hydroxy-4-triacontencoic acid.
Examples of the new di-unsaturated 2-hydroxyalkenoic acids, where R
is C.sub.y H.sub.2y-1 include:
2-Hydroxy-4,7-octadienoic acid
2-Hydroxy-4,9-decadienoic acid
2-Hydroxy-4,10-undecadienoic acid
2-Hydroxy-4,11-dodecadienoic acid
2-Hydroxy-4,13-tetradecadienoic acid
2-Hydroxy-4,15-hexadecadienoic acid
2-Hydroxy-4,17-octadecadienoic acid
2-Hydroxy-4,19-eicosadienoic acid
2-Hydroxy-4,21-docosadienoic acid
2-Hydroxy-4,23-tetracosadienoic acid
2-Hydroxy-4,25-hexacosadienoic acid
2-Hydroxy-4,27-octacosadienoic acid, and
2-Hydroxy-4,29-triacontadienoic acid.
Examples of new mono unsaturated oxa-2-hydroxyalkenoic acids where
R is C.sub.y H.sub.2y OZ (ether acids) include:
2-Hydroxy-6-oxa-4-heptenoic acid
2-Hydroxy-7-oxa-4-octenoic acid
2-Hydroxy-9-oxa-4-decenoic acid
2-Hydroxy-9-oxa-4-undecenoic acid
2-Hydroxy-11-oxa-4-dodecenoic acid
2-Hydroxy-13-oxa-4-tetradecenoic acid
2-Hydroxy-13-oxa-4-pentadecenoic acid
2-Hydroxy-14-oxa-4-pentadecenoic acid
2-Hydroxy-13-oxa-14-methyl-4-pentadecenoic acid
2-Hydroxy-11,14-dioxa-4-pentadecenoic acid
2-Hydroxy-13-oxa-4-hexadecenoic acid
2-Hydroxy-14-oxa-4-hexadecenoic acid
2-Hydroxy-15-oxa-4-hexadecenoic acid
2-Hydroxy-17-oxa-4-octadecenoic acid
2-Hydroxy-14,17-dioxa-4-octadecenoic acid
2-Hydroxy-18-oxa-4-eicosenoic acid
2-Hydroxy-18-oxa-19-methyl-4-eicosenoic acid
2-Hydroxy-19-oxa-4-docosenoic acid
2-Hydroxy-18,21-dioxa-4-tricosenoic acid
2-Hydroxy-22-oxa-4-tetracosenoic acid
2-Hydroxy-25-oxa-4-hexacosenoic acid
2-Hydroxy-24-oxa-4-heptacosenoic acid
2-Hydroxy-25-oxa-4-octacosenoic acid
2-Hydroxy-23,26-dioxa-4-octacosenoic acid, and
2-Hydroxy-29-oxa-4-triacontenoic acid.
It is to be understood that the above examples of 2-hydroxyalkenoic
acids are merely illustrative of the many acids covered by the
generic structure (1) given herein before.
PROCESS FOR PREPARING THE 2-HYDROXYALKENOIC ACID
The process for preparing the 2-hydroxyalkenoic acids, as herein
defined, is based on that described by Klimova et al, in a paper
entitled "Catalytic monoene synthesis with carbonyl compounds.
Addition of 1-alkenes to glyoxylic acid esters", published in Dokl.
Akad. Nauk SSSR 173 (6), 1332-5 (1967) and abstracted in Chem Abs
67 (1967), 108156c.
The process according to the invention therefore comprises, in
broad general terms, the steps of catalysing the reaction of an
alkene and an alkyl glyoxalate to form, as an intermediate, a
2-hydroxyalkenoate ester, and subsequently hydrolysing this ester
with a base in order to form the corresponding free
2-hydroxyalkenoic acid.
A preferred process for preparing the 2-hydroxy alkenoic acids
according to the invention involves the use of methyl glyoxalate,
as the alkyl glyoxalate, and stannic chloride as the catalyst, the
alkene having the structure (2) ##STR4## the options for the group
R being as herein defined for R in structure (1).
This aspect of the invention can accordingly be defined as a
process for preparing a 2-hydroxyalkenoic acid, as defined herein,
and having the structure (1), which process comprises the steps
of:
i) catalysing the reaction of an alkene having the structure (2):
##STR5## with an alkyl glyoxalate having the structure (3) ##STR6##
where R"' is C.sub.m H.sub.2m+1 and m is an integer of from 1 to 4;
to form an unsaturated hydroxy ester having the structure (4)
##STR7## and ii) hydrolysing the unsaturated hydroxy ester to yield
the corresponding 2-hydroxy alkenoic acid having the structure (1)
##STR8##
The steps of a preferred form of this process can be summarised as
follows:
i. Dissolve methyl glyoxalate and the alkene in dichloromethane
under nitrogen atmosphere and cool;
ii. Add stannic chloride, stir and allow to warm;
iii. Neutralise with triethylamine, add water and further
dichloromethane;
iv. Separate organic layer, wash, dry, remove solvent and distill
off ester product;
v. Hydrolyse ester with base under reflux conditions; and
vi. Wash solution with hexane, acidify solution and extract
product, dry and then remove organic solvent to leave either liquid
(purifiable by distillation) or solid (purifiable by
crystallisation).
According to a preferred process, employing the above summary, the
hydroxyalkenoic acids according to the invention can be prepared as
follows:
Methyl glyoxalate (1.0 equivalents) and the requisite alkene (2.0
equivalents) are dissolved in dry dichloromethane under a nitrogen
atmosphere. Stannic chloride (0.3 equivalents) is added dropwise
with stirring and cooling (ice/water bath at approx 0.degree. C.).
After 30 minutes at this temperature, the reaction is allowed to
warm to room temperature and stirred for a further 21 hours. The
mixture is neutralised with triethylamine (0.3 equivalents),
stirred for an additional 5 minutes before water and
dichloromethane are added. The organic layer is separated, washed
in turn with water and brine, dried over anhydrous magnesium
sulphate and evaporated, with the crude product being purified by
short path distillation to give the pure hydroxy ester.
This intermediate is treated with 20% w/v sodium hydroxide solution
(water:methanol, 1:1) and heated under reflux for 1 hour. After the
reaction mixture has cooled to room temperature, it is washed with
hexane and the organic layer separated. The clear aqueous phase is
acidified to pH 1 with concentrated hydrochloric acid, followed by
extraction of product with diethylether. The organic layer is
separated, washed with brine, dried over anhydrous magnesium
sulphate and evaporated to dryness to yield the desired
2-hydroxy-4-alkenoic acid.
These aspects of the invention are further illustrated by the
following Examples which describe synthesis of selected
2-hydroxy-4-alkenoic acids according to the invention and provide
also characterising data of these new acids.
EXAMPLE 1
Synthesis of 2-Hydroxy-4-octadecenoic acid (5)
The synthesis of this acid is in accordance with the following
scheme, in which hexadecene (6) is the alkene starting material.
##STR9##
i. Synthesis of the intermediate methyl
2-hydroxy-4-octadecenoate
Methyl glyoxalate (8.80 g, 0.1 mol, 1.0 eq) and 1-hexadecene (44.80
g, 0.2 mol, 2.0 eq) are dissolved in dry dichloromethane (200 ml,
freshly distilled from calcium hydride) under a nitrogen
atmosphere. Stannic chloride (3.51 ml, 0.03 mol, 0.3 eq) is added
dropwise with stirring and cooling at 0.degree. C. (ice/water
bath). After half an hour the reaction mixture is allowed to warm
to room temperature and stirred for a further 21 hours before being
neutralised with triethylamine (4.2 ml, 0.03 mol, 0.3 eq) with a
further 5 minutes stirring. Water (50 ml) and dichloromethane (100
ml) are added, the organic layer is separated, washed in turn with
water (50 ml) and brine (50 ml), dried over anhydrous magnesium
sulphate and evaporated. The crude oil is purified by short path
distillation (bp 220-230.degree. C./0.7 mm Hq) to furnish the ester
product as a colourless liquid.
ii. Synthesis of 2-hydroxy-4-octadecenoic acid having the structure
(5)
Methyl 2-hydroxy 4-octadecenoate (8.21 g, 0.026 mol, 1.0 eq) is
heated under reflux with a large excess of sodium hydroxide (8.4 g,
0.21 mol, 8.1 eq) in water (20 ml) and methanol (20 ml) for 1 hour.
After cooling down to room temperature, the mixture is washed with
hexane (50 ml) and the organic phase separated. The clear aqueous
layer is acidified to pH 1 with concentrated hydrochloric acid and
the resultant mixture is extracted with diethylether (3.times.50
ml), the combined organic layers being washed with brine (50 ml)
dried over anhydrous magnesium sulphate and evaporated to give a
white solid. This is recrystallised from ethyl acetate/hexane to
give the product acid (5) as white needles, 6.35 g (81%), mp
78-79.5.degree. C.
Characterising spectral data were as follows:
mp 78-79.5.degree. C.; .sup.v max (nujol) 3440 and 1745 cm.sup.-1 ;
.delta..sub.H (360 MHz, d.sub.6 -DMSO) 0.90 (3H, t, 18-H.sub.3,
CH.sub.3), 1.30 (22H, br s, 7 to 17-H.sub.2, CH.sub.2), 2.05 (2H,
m, 6-H.sub.2, CH.sub.2 CH.dbd.), 2.25-2.40 (2H, 2xm, 3-H.sub.2,
CH.sub.2 CHOH), 4.00 (1H, t, 2-H, CHOH) and 5.50 p.p.m. (2H, m, 4
and 5-H, CH.dbd.); C.I., M.sup.+ 298.
EXAMPLE 2
Synthesis of 2-hydroxy-4,9-decadienoic acid (7)
The synthesis of this acid is in accordance with the following
scheme, in which 1,7-octadiene (8) is the alkene starting material.
##STR10##
The procedure for the synthesis of methyl
2-hydroxy-4,9-decadienoate, and its conversion to
2-hydroxy-4,9-decadienoic acid were essentially as described in
Example 1, except that 1,7-octadiene was used as the alkene in
place of hexadecene.
2-Hydroxy-4,9-decadienoic acid had a boiling point of
240-250.degree. C. at 0.6 mm Hg, and possessed the following
characterising spectral data:
.sup.v max (liq film) 3500-2400 (br), 2950, 2920, 1725 (br), 1640,
1440, 1380, 1210, 1100, 990, 970 and 720 cm.sup.-1 ; .delta..sub.H
(360 MHz, CDCl.sub.3) 1.45 (2H, m, 7-H.sub.2, CH.sub.2), 2.05 (4H,
m, 6 and 8-H , CH.sub.2 CH.dbd.), 2.40 (1H, m, 3-H, CHCHOH), 2.60
(1H, m, 3-H, CHCHOH), 4.30 (1H, t, J=3.3 Hz, 2-H, CHOH), 5.00 (2H,
m, 8-H.sub.2, CH.sub.2 .dbd.), 5.40 (1H, m, 5-H, CH.dbd.), 5.65
(1H, m, 4-H, CH.dbd.) and 5.85 p.p.m. (1H, m, 7-H, CH.dbd.), C.I.;
M.sup.+ 184.
EXAMPLE 3
Synthesis of 2-hydroxy-13-oxa-4-tetradecenoic acid (9)
The synthesis of this acid is in accordance with the following
scheme, in which 11-oxa-1-dodecene (10) is the alkene starting
material. ##STR11##
The procedure for the synthesis of methyl
2-hydroxy-13-oxa-4-tetradecenoate and its conversion to
2-hydroxy-13-oxa-4-tetradecenoic acid were essentially as described
in Example 1, except that 11-oxa-1-dodecene was used as the alkene
in place of hexadecene.
2-Hydroxy-13-oxa-4-tetradecenoic acid had a melting point of
5-10.degree. C., and possessed the following characterising
spectral data:
.sup.v max (liq film) 3400, 2930, 2860, 1720, 1250, 1100 and 970
cm.sup.-1 ; .delta..sub.H (360 MHz, CDCl.sub.3) 1.25 (8H, br m, 7
to 10-H.sub.2, CH.sub.2), 1.55 (2H, m, 11-H.sub.2, CH.sub.2
CH.sub.2 O), 2.00 (2H, m, 6-H, CH.sub.2 CH.dbd.), 2.40-2.60 (2H,
2.times.m, 3-H.sub.2, CH.sub.2, CHOH), 3.35 (3H, s, 14-H.sub.3,
CH.sub.3 O), 3.40 (2H, t, 2-H.sub.2, CH.sub.2 O), 4.30 (1H, t, 2-H,
CHOH) and 5.40-5.65 p.p.m. (2H, 2.times.m, 4 and 5-H, CH.dbd.);
C.I., M.sup.+ 244.
As mentioned, the invention also relates to a composition for
topical application to human skin which comprises 2-hydroxy
alkenoic acids, including both new acids as herein defined and
other acids already reported in scientific literature, but whose
utility is far removed from use in topical products.
As mentioned above, difficulty can be experienced when formulating
certain 2-hydroxyalkenoic acids in skin cosmetic, formulations, due
to their poor solubility in water.
It has now surprisingly been discovered that certain
2-hydroxyalkenoic acids are much more soluble in water and are
considerably easier to formulate than their corresponding saturated
acids. Furthermore, topical application of these unsaturated acids
to skin results in a substantial increase in skin flexibility, so
that the pliability of the skin is improved.
The invention also concerns compositions containing the new
2-hydroxyalkenoic acids, as herein defined, which are suited to
topical application to human skin, hair and nails. The invention is
also concerned with compositions of a similar nature, and having a
similar use, that comprise 2-hydroxyalkenoic acids whose identity
have been disclosed in published literature, but whose reported
utility is far removed from personal care products intended for
topical application to human skin.
DEFINITION OF THE COMPOSITION OF THE INVENTION
The invention also provides a composition for topical application
to human skin, hair or nails which comprises:
i. from 0.1 to 99.9% by weight of a 2-hydroxyalkenoic acid having
the structure (20) ##STR12## where
R' is chosen from:
a. C.sub.w H.sub.2w,
b. C.sub.y H.sub.2y-1, and
c. C.sub.y H.sub.2y OZ
where
Z is chosen from H, R" and (CH.sub.2).sub.n OR"
R" is chosen from C.sub.m H.sub.2m+1 and (CH.sub.2).sub.n OC.sub.m
H.sub.2m+1 ;
w is an integer of from 1 to 25
y is an integer of from 2 to 25
m is an integer of from 1 to 4
n is an integer of from 1 to 6; and
ii. from 0.1 to 99.9% by weight of a cosmetically acceptable
vehicle for the acid.
The 2-hydroxyalkenoic acid
The composition according to the invention comprises a
2-hydroxyalkenoic acid or a mixture thereof, having the structure
(20) as herein defined.
Examples of these 2-hydroxyalkenoic acids include:
2-hydroxy-4-hexenoic acid
2-hydroxy-4-heptenoic acid,
2-hydroxy-4-octenoic acid, and
2-hydroxy-4-dodecenoic acid.
Further examples of 2-hydroxyalkenoic acids, include the new
mono-saturated acids, di-unsaturated acids and mono-unsaturated
oxo-acids as herein defined.
The 2-hydroxyalkenoic acid is present in the composition according
to the invention in an amount of from 0.1 to 90%, preferably from
0.5 to 10% and ideally from 1 to 5% by weight of the
composition.
Synthesis of 2-hydroxyalkenoic acid
The 2-hydroxyalkenoic acids for use in the composition according to
the invention can be prepared by the method described hereinbefore
for the new 2-hydroxyalkenoic acids.
This aspect of the invention is illustrated by two more Examples
which describe the synthesis and characterisation of two further
2-hydroxyalkenoic acids having the structure (20).
EXAMPLE 4
Synthesis of 2-Hydroxy-4-octenoic acid (21)
The synthesis of this acid is in accordance with the following
scheme, in which 1-hexene (22) is the alkene starting material
which is reacted with methyl glyoxalate to form methyl
2-hydroxy-4-octenoate (23) and then hydrolysed to form the free
acid (21): ##STR13##
i. Synthesis of methyl 2-hydroxy-4-octenoate (23)
Methyl glyoxalate (8.80 g, 0.1 mol, 1.0 eq) and 1-hexene (16.80 g,
0.2 mol, 2.0 eq) are dissolved in dry dichloromethane (150 ml,
freshly distilled from calcium hydride) under a nitrogen
atmosphere. Stannic chloride (3.51 ml, 0.03 mol, 0.3 eq) is added
dropwise with stirring and cooling at 0.degree. C. (ice/water
bath). After half an hour the reaction mixture is allowed to warm
to room temperature and stirred for a further 21 hours before being
neutralised with triethylamine (4.2 ml, 0.03 mol, 0.3 eq) with a
further 5 minutes stirring. Water (50 ml) and dichloromethane (100
ml) are added, the organic layer is separated, washed in turn with
water (50 ml) and brine (50 ml), dried over anhydrous magnesium
sulphate and evaporated. The crude oil is purified by short path
distillation (b p 120-130.degree. C./0.7 mm Hg) to furnish the
ester product (23) as a colourless liquid, 11.49 g (67% yield).
Characterisation spectral data were as follows: .sup.v max (liq
film) 3 500 (br), 2 960, 2 920, 1740, 1 440, 1 2110 (br), 1090 and
970 cm.sup.-1 ; .delta..sub.H (360 MH.sub.z, CDCl.sub.3) 0.90 (3H,
t, J=8.0 Hz, 8-H.sub.3, CH.sub.3 CH.sub.2), 1.40 (2H, m, 7-H.sub.2,
CH.sub.2 CH.sub.3), 2.00 (2H, m, 6-H.sub.2, CH.sub.2 CH.dbd.), 2.40
(1H, m, 3-H, CHCHOH), 2.50 (1H, m, 3-H, CHCHOH), 2.75 (1H, d, J=6.5
Hz, OH), 3.80 (3H,s, CH.sub.3 O), 4.25 (1H, m, 2-H, CHOH), 5.40
(1H, m, 5-H, CH.dbd.) and 5.60 p.p.m. (1H, m, 4-H, CH.dbd.); C.I.,
M.sup.+ 172.
ii. Synthesis of 2-hydroxy-4-octenoic acid (21)
Methyl 2-hydroxy-4-octenoate (23)(7.04 g, 0.041 mol, 1.0 eq) is
heated under reflux with a large excess of sodium hydroxide (13.5
g, 0.34 mol, 8.3 eq) in water (30 ml) and methanol (30 ml) for 1
hour. After cooling down to room temperature, the mixture is washed
with hexane (50 ml) and the organic phase separated. The clear
aqueous layer is acidified to pH 1 with concentrated hydrochloric
acid and the resultant mixture is extracted with diethylether
(3.times.50 ml), the combined organic layers being washed with
brine (50 ml) thence dried over anhydrous magnesium sulphate and
evaporated to give a colourless oil which slowly crystallised to
furnish the product acid (21) as a white waxy solid, 5.72 g (88%),
m p 37-38.degree. C.
Characterisation spectral data were as follows: .sup.v max (nujol)
3440, 2 820, 1695, 1420, 1150, 1095, 1045 and 920 cm.sup.-1 ;
.delta..sub.H (360 MH.sub.z, CDCl.sub.3) 0.90 (3H, t, 8-H,
CH.sub.3), 1.40 (2H, m, 7-H.sub.2, CH.sub.3 CH.sub.2), 2.00 (2H, m,
6-H.sub.2, CH.sub.2 CH.dbd.), 2.40-2.60(2H,m,3-H.sub.2, CH.sub.2
CHOH), 4.30 (1H, t, CHOH), 5.40 (1H, m, 5-H, CH.dbd.) and 5.60
p.p.m. (1H, m, 4-H, CH.dbd.); C.I., M.sup.+ 158.
EXAMPLE 5
Synthesis of 2-Hydroxy-4-dodecenoic acid (24)
The synthesis of this acid is in accordance with the following
scheme, in which 1-decene (25) is the alkene starting material.
##STR14##
The procedure for the synthesis of methyl 2-hydroxy-4-dodecenoate,
and its conversion to 2-hydroxy-4-dodecenoic acid were essentially
as described in Example 4, except that 1-decene was used on the
alkene in place of 1-hexene.
2-Hydroxy-4-dodecenoic acid had a melting point of 45-48.degree. C.
and possessed the following characterising spectral data:
.sup.v max (nujol) 3440, 3200-2500 (br), 1740, 1090, 965 and 720
cm.sup.-1 ; .delta..sub.H (360 MH.sub.z, CDCl.sub.3) 0.90 (3H, t,
12-H.sub.3, CH.sub.3), 1.20-1.40 (10 H, m, 7 to 11-H.sub.2,
CH.sub.2), 2.00 (2H, m, 6-H.sub.2, CH.sub.2 CH.dbd.), 2.45 (1H, m,
3-H, CHCHOH), 2.55 (1H, m, 3-H, CHCHOH), 4.30 (1H, t, 2-H, CHOH),
5.40 (1H, m, 5-H, CH.dbd.) and 5.60 p.p.m. (1H, m, 4-H, CH.dbd.);
F.A.B., M.sup.+ 214.
The Cosmetically Acceptable Vehicle
The composition according to the invention also comprises a
cosmetically acceptable vehicle, the selection of which will depend
on the required product form of the composition. Typically, the
vehicle will be chosen from diluents, dispersants or carriers for
the 2-hydroxyalkenoic acid, so as to ensure an even distribution of
it when applied to the skin.
Compositions according to this invention can include water as a
vehicle, usually with at least one other cosmetically-acceptable
vehicle.
Vehicles other than water that can be used in compositions
according to the invention can include liquids or solids as
emollients, solvents, humectants, thickeners and powders. Examples
of each of these types of vehicles, which can be used singly or as
mixtures of one or more vehicles, are as follows:
Emollients, such as stearyl alcohol, glyceryl monoricinoleate,
glyceryl monostearate, propane-1,2-diol, butane-1,3-diol, mink oil,
cetyl alcohol, isopropyl isostearate, stearic acid, isobutyl
palmitate, isocetyl stearate, oleyl alcohol, isopropyl laurate,
hexyl laurate, decyl oleate, octadecan-2-ol, isocetyl alcohol,
eicosanyl alcohol, behenyl alcohol, cetyl palmitate, silicone oils
such as dimethylpolysiloxane, di-n-butyl sebacate, isopropyl
myristate, isopropyl palmitate, isopropyl stearate, butyl stearate,
polythylene glycol, triethylene glycol, lanolin, cocoa butter, corn
oil, cotton seed oil, tallow, lard, olive oil, palm kernel oil,
rapeseed oil, safflower seed oil, soybean oil, sunflower seed oil,
olive oil, sesame seed oil, coconut oil, arachis oil, castor oil,
acetylated lanolin alcohols, petroleum, mineral oil, butyl
myristate, isostearic acid, palmitatic acid, isopropyl linoleate,
lauryl lactate, myristyl lactate, decyl oleate, myristyl
myristate;
Propellants, such as trichlorofluoromethane,
dichlorodifluoromethane, dichlorotetrafluoroethane,
monochlorodifluoromethane, trichlorotrifluoroethane, propane,
butane, isobutane, dimethyl ether, carbon dioxide, nitrous
oxide;
Solvents, such as ethyl alcohol, methylene chloride, isopropanol,
acetone, castor oil, ethylene glycol monoethyl ether, diethylene
glycol monobutyl ether, diethylene glycol monoethyl ether, dimethyl
sulphoxide, dimethyl formamide, tetrahydrofuran;
Humectants, such as glycerin, sorbitol, sodium
2-pyrrolidone-5-carboxylate, soluble collagen, dibutyl phthalate,
gelatin;
Powders, such as chalk, talc, fullers earth, kaolin, starch, gums,
colloidal silicon dioxide, sodium polyacrylate, tetra alkyl and/or
trialkyl aryl ammonium smectites, chemically modified magnesium
aluminium silicate, organically modified montmorillonite clay,
hydrated aluminium silicate, fumed silica, carboxyvinyl polymer,
sodium carboxymethyl cellulose, ethylene glycol monostearate.
The cosmetically acceptable vehicle will usually form from 10 to
99.9%, preferably from 50 to 99% by weight of the composition, and
can, in the absence of other cosmetic adjuncts, form the balance of
the composition.
Cosmetic Adjuncts
Examples of other conventional adjuncts, some of which can also
function as vehicles, that may optionally be employed, include
volatile and non-volatile silicones; silicone polymers;
preservatives, such as para-hydroxy benzoate esters; humectants,
such as butane-1,3 -diol, glycerol, sorbitol, polyethylene glycol;
stabilisers, such as sodium chloride or ammonium chloride; buffer
system, such as lactic acid together with a base such as sodium
hydroxide; oils and waxes, such as avocado oil, Evening Primrose
oil, sunflower oil, beeswax, ozokerite wax, paraffin wax, lanolin,
lanolin alcohol; emollients; thickeners; activity enhancers;
colourants; whiteners; perfumes; emulsifiers; sunscreens;
bactericides and water.
Cosmetic adjuncts can form up to 50% by weight of the composition
and can conveniently form the balance of the composition.
Process for preparing the composition
The invention also provides a process for the preparation of a
composition for topical application to human skin which comprises
the step of incorporating the 2-hydroxyalkenoic acid, as herein
defined, into the composition, together with a cosmetically
acceptable vehicle.
Use of the composition
The composition according to the invention is intended primarily as
a product for topical application to human skin, particularly dry
skin, when repeated application can alleviate the dry condition,
and restore the skin to a more natural, soft, supple, healthy
state. The composition can also be used to treat the hair,
including the scalp, and finger and toe nails.
In use, a small quantity of the composition, for example from 1 to
5 ml, is applied to the affected area of skin, hair or nails, from
a suitable container or applicator and, if necessary, it is then
spread over and/or rubbed into the skin, hair or nails using the
hand or fingers or a suitable device.
PRODUCT FORMS AND PACKAGING
The topical skin treatment composition of the invention can be
formulated as a fluid, for example in a product such as a lotion,
with or without an applicator such as a roll-ball applicator, or a
propellant driven aerosol device or a container fitted with a pump
to dispense the composition, for example as a mousse or simply for
storage in a non-deformable bottle or squeeze container.
Alternatively, the composition of the invention may be solid for
example, as a bar or tablet, such as a soap bar, or semi-solid, for
example as a cream, lotion, gel or ointment, for use in conjunction
with a suitable applicator, or simply for storage in a tube or
lidded jar.
The invention accordingly also provides a closed container
containing a cosmetically acceptable composition as herein
defined.
EVIDENCE OF THE SUPERIORITY OF THE INVENTION
The following experiments compare the extensibility of the stratum
corneum when treated either with the 2-hydroxyalkenoic acid of the
invention or with certain corresponding 2-hydroxyalkanoic
acids.
Measurements of extensibility were made as described in EP-A 0 007
785. For each sample of stratum corneum, an extensibility ratio was
calculated as the ratio of the extensibility measurement for a
treated sample to the measurement for an untreated control
sample.
EXPERIMENT 1
In accordance with this technique, an in vitro extensibility study
was carried out on stratum corneum samples from guinea pig foot
pads. Measurements of extensibility were made at a relative
humidity of 62% and a temperature of 22.degree. C. on batches of
six samples of stratum corneum. These samples were treated with
0.06M aqueous solution of an acid maintained at pH 4.0 with sodium
hydroxide.
The results are detailed in Table 1 below.
TABLE 1 ______________________________________ All results are at
0.06M concentration and at pH 4.0 Extensibility Relative Acid Ratio
Ratio ______________________________________ 2-Hydroxyoctanoic 1.30
1.00 2-Hydroxypropionic (lactic) 1.24 0.95 2-Hydroxydecanoic 1.24
0.95 2-Hydroxydodecanoic 1.28 0.98 2-Hydroxy-4-decenoic 1.50 1.15
2-Hydroxy-4-dodecenoic 1.46 1.12 2-Hydroxy-4,9-decadienoic 1.72
1.32 2-Hydroxy-4,11-dodecadienoic 1.52 1.17
______________________________________
The value for distilled water at pH 4.0 is approximately unity. It
is evident that the use of the 2-hydroxyalkenoic acids leads to an
increase in the ratio of up to 32% when compared to the use of the
best 2-hydroxyalkanoic acid, i.e. 2-hydroxyoctanoic acid.
EXPERIMENT 2
This experiment compares the increase in extensibility conferred by
aqueous solutions of acids at low pH. The tests were carried out on
heat-separated guinea-pig footpads which were immersed in the
required solution at the specified pH value. The extensibility
ratios are shown in Table 2.
TABLE 2 ______________________________________ Extensibility Acid
Concn. pH Relative ______________________________________
2-Hydroxypropionic 0.20M 2.5 3.00 .+-. 0.65 2-Hydroxyoctanoic 0.20M
2.5 5.90 .+-. 0.75 2-Hydroxy-13-oxa-4- 0.12M 2.9 12.35 .+-. 4.33
tetradecenoic ______________________________________
The extensibility ratio for the 2-hydroxy-13-oxa-4-tetradecenoic
acid is significantly greater at the 99% confidence level than that
of the 2-hydroxypropionic acid. The elasticity effect of this oxa
acid is also significantly greater at the 98% confidence level than
that of the 2-hydroxyoctanoic acid. Both the shorter acids were
evaluated at a lower pH value and a higher concentration and still
appear inferior to the oxa acid.
EXPERIMENT 3
This experiment compares the extensibility increase conferred
in-vitro by solutions of several 2-hydroxyalkenoic acids against
that conferred by 2-hydroxy octanoic acid. The tests were carried
out on heat-separated guinea-pig footpads which were immersed in
the required solution maintained at pH 4.0 by the addition of
sodium hydroxide solution. The extensibility ratios for each group
of samples are shown in Table 3.
TABLE 3 ______________________________________ Extensibility
Relative Significance Acid Ratio Ratio Level
______________________________________ part i) All the following
results are at 0.06M concentration. 2-Hydroxy octanoic 1.30 .+-.
0.27 1.00 -- 2-Hydroxy-13-oxa- 2.53 .+-. 0.72 1.95 98%
4-pentadecenoic 2-Hydroxy-14-oxa- 3.02 .+-. 0.82 2.23 99%
4-pentadecenoic 2-Hydroxy-14-oxa- 2.46 .+-. 0.63 1.89 99%
4-hexadecenoic 2-Hydroxy-14,17- 3.73 .+-. 1.78 2.87 95% dioxa-4-
octadecenoic ______________________________________ Part ii) All
the following results are at 0.12M concentration. 2-Hydroxy
octanoic 2.79 .+-. 0.71 1.00 -- 2-Hydroxy-13-oxa-4- 4.49 .+-. 0.83
1.61 98% tetradecenoic 2-Hydroxy-13-oxa-4- 4.88 .+-. 1.22 1.75 98%
pentadecenoic 2-Hydroxy-14-oxa-4- 4.44 .+-. 0.47 1.59 99%
hexadecenoic 2-Hydroxy-14,17- 5.44 .+-. 1.47 1.95 98% dioxa-4-
octadecenoic ______________________________________
EXPERIMENT 4
This experiment compares the elasticity effect conferred by an
aqueous solution of an unsaturated acid with that conferred by an
aqueous solution of the saturated equivalent acid. The evaluation
was performed on heat-separated guinea-pig footpads which were
immersed in the required solution maintained at pH 4.0. The results
are shown in Table 4.
TABLE 4 ______________________________________ All the following
results are at 0.12M concentration. Extensibility Relative Acid
Ratio Ratio ______________________________________ 2-Hydroxy-14-oxa
pentadecanoic 1.76 .+-. 0.54 -- 2-Hydroxy-14-oxa-4- 4.88 .+-. 1.22
2.77 pentadecenoic ______________________________________
The extensibility ratio for the 2-hydroxyalkenoic acid
[2-hydroxy-14-oxa-4-pentadecenoic acid] is significantly greater at
the 99% confidence level than that of the corresponding
2-hydroxyalkanoic acid [2-hydroxy-14-oxa-pentadecanoic acid].
EXAMPLES
Cosmetic Compositions
The invention is further illustrated by the following examples.
EXAMPLE 6
The example illustrates an oil-continuous (W/O) cream containing
2-hydroxy-4-tetradecenoic acid.
______________________________________ Ingredients % w/w
______________________________________ Silicone oils 24.00 Whitener
0.15 Humectants 5.00 2-Hydroxy-4 tetradecenoic acid 1.00 Lactic
acid 5.00 Potassium hydroxide 4.00 Water 60.85 100.00
______________________________________
The skin cream, having a pH value of 5, is made by the process, as
herein described, by adding gradually to a mixture of silicones and
whitener an aqueous mixture of the remaining ingredients and
homogenising.
EXAMPLE 7
This example illustrates an oil-continuous w/o cream containing
2-hydroxy-13-oxa-4-pentadecenoic acid, evening primrose oil and
sunscreens.
______________________________________ Ingredients % w/w
______________________________________ Silicone oils 25.00 Whitener
0.15 Evening Primrose Oil 3.00 Humectants 5.00 Sunscreens 4.00
2-Hydroxy-13-oxa-4-pentadecenoic acid 1.50 Sodium hydroxide 2.00
Sodium chloride 2.00 Lactic acid 5.00 Water 52.35 100.00
______________________________________
The skin cream, having a pH value of 4.5, is made by the process,
as herein described, by adding gradually to a mixture of silicones
and whitener an aqueous mixture of the remaining ingredients and
homogenising.
EXAMPLE 8
This example illustrates a oil-continuous (w/o) gel containing
2-hydroxy-4-dodecenoic acid.
______________________________________ Ingredients % w/w
______________________________________ Emulsifiers 20.00 Silicone
oils 20.00 Humectant 11.00 2-Hydroxy-4-dodecenoic acid 1.00 Sodium
hydroxide 4.55 Lactic acid 5.00 Water 38.45 100.00
______________________________________
The gel, having a pH value of 5.5, is made by the process, as
herein described, by adding to the silicone oils an aqueous mixture
of the remaining ingredients and homogenising.
EXAMPLE 9
This example illustrates a water-continuous (o/w) cream containing
a 2-hydroxy-4-decenoic acid.
______________________________________ Ingredients % w/w
______________________________________ Thickener 0.50 Whitener 0.15
Humectant 13.50 Emulsifiers 10.35 Silicone oil 7.60
2-Hydroxy-4-decenoic acid 1.00 Sodium Hydroxide 5.00 Lactic Acid
3.00 Water 58.90 100.00 ______________________________________
The skin cream, having a pH value of 4, is made by the process, as
herein described, by adding to a heated mixture of the thickener,
humectant and 75% of the water. The remaining ingredients are added
as an aqueous mixture with further homogenising.
EXAMPLE 10
This example illustrates a water-continuous (o/w) cream containing
2-hydroxy-4,11-dodecadienoic acid, evening primrose oil and
sunscreens.
______________________________________ Ingredients % w/w
______________________________________ Thickener 0.50 Whitener 0.20
Humectant 10.00 Evening Primrose Oil 2.00 Sunscreens 3.00
Emulsifiers 10.50 Silicone oil 7.60 2-Hydroxy-4,11-dodecadienoic
acid 1.00 Triethanolamine 6.00 Lactic acid 4.00 Water 55.20 100.00
______________________________________
The skin cream, having a pH value of 6, is made by the process, as
herein described, by adding to a heated mixture of emulsifiers,
silicone oil and whitener a mixture of the thickener, humectant and
75% of the water and homogenising. The remaining ingredients are
added as an aqueous mixture with further homogenising.
EXAMPLE 11
The example illustrates a night cream containing
2-hydroxy-4,21-docosadienoic acid and beeswax.
______________________________________ Incredients % w/w
______________________________________ Silicone oil 21.00
Emulsifiers 15.25 Beeswax 8.00 Lanolin 2.50
2-Hydroxy-4,21-docosadienic acid 2.00 Potassium hydroxide 5.00
Water 46.25 100.00 ______________________________________
The night cream, having a pH value of 6.5, is made by the process,
as herein described, by adding to a mixture of emulsifiers,
silicone oil, beeswax and lanolin, a mixture of the remaining
ingredients and homogenising.
EXAMPLE 12
This example illustrates a lotion suitable for application to the
hands containing 2-hydroxy-4-octenoic acid and lanolin.
______________________________________ Ingredient %
______________________________________ Emulsifiers 10.00 Lanolin
2.50 2-Hydroxy-4-octenoic acid 3.00 Trethanolamine 4.50 Water 80.00
100.00 ______________________________________
EXAMPLE 13
This example illustrates a water-continuous (o/w) hand and body
lotion containing 2-hydroxy-17-oxa-4-octadecenoic acid.
______________________________________ Ingredient %
______________________________________ Emulsifiers 3.00 Silicone
oil 5.00 Thickener 0.35 Humectant 9.45
2-Hydroxy-17-oxa-4-octadecenoic acid 1.50 Ammonium hydroxide 3.95
Ammonium chloride 2.00 Water 74.75 100.00
______________________________________
EXAMPLE 14
This example illustrates a wash-off/wipe-off cleansing cream
containing 2-hydroxy-4-hexenoic acid and chamomile.
______________________________________ Ingredient %
______________________________________ Mineral oil 10.00 Emulsifier
3.00 Chamomile distillate 0.50 2-Hydroxy-4-hexenoic acid 1.00
Triethanolamine 2.80 Water 82.70 100.00
______________________________________
EXAMPLE 15
This example illustrates a wash-off/wipe-off cleansing lotion
containing 2-hydroxy-4,15-hexadecadienoic acid and beeswax.
______________________________________ Ingredient % w/w
______________________________________ Mineral oil 45.00 Emulsifier
3.20 Beeswax 8.00 Thickener 10.00 Perfume 0.20
2-Hydroxy-4,15-hexadecadienoic acid 1.00 Triethanolamine 4.00 Water
28.60 100.00 ______________________________________
The cleansing lotion, having a pH of 5.5, is made by the process,
as herein described, by adding to a mixture of emulsifier, mineral
oil and beeswax a mixture of the remaining ingredients and
homogenising.
EXAMPLE 16
The example illustrates a facial-washing foam containing
2-hydroxy-23,26-dioxa-4-octacosenoic acid and azulene.
______________________________________ Ingredient % w/w
______________________________________ Emulsifier 20.00 Thickener
3.00 Foam Booster 25.00 Humectant 10.00 Azulene crystals 0.25
Bentone 0.50 2-Hydroxy-23,26-dioxa-4-octacosenoic 2.50 acid
Potassium hydroxide 4.50 Water 34.25 100.00
______________________________________
EXAMPLE 17
This example illustrates a conventional soap bar containing
2-hydroxy-4-docosenoic acid.
______________________________________ Ingredient % w/w
______________________________________ Anionic detergent 18.00 Foam
aid 8.00 Sodium hydroxide 12.00 Hardening agent 2.00 Alkaline
silicate 2.00 Calcite 12.00 Talc 10.00 2-Hydroxy-4-docosenoic acid
2.00 Water 34.00 100.00 ______________________________________
EXAMPLE 18
This example illustrates an all-purpose face-mask containing
2-hydroxy-4-hexacosenoic acid and phytoconcentrol camomile.
______________________________________ Ingredient % w/w
______________________________________ Kaolin 30.00 Mineral oil
10.00 Paraffin wax 10.00 Bentonite 4.00 2-Hydroxy-4-hexacosenoic
acid 1.40 Sodium hydroxide 4.20 Phytoconcentrol camomile 0.25 Water
40.15 100.00 ______________________________________
The mask is made by the process, as herein described, by blending
the mixture of the ingredients.
EXAMPLE 19
This example illustrates a solution used to condition hair
containing 2-hydroxy-4-hexadecenoic acid.
______________________________________ Ingredient % w/w
______________________________________ Emulsifier 0.80
2-Hydroxy-4-hexadecenoic acid 0.50 Sodium chloride 0.50 Sodium
hydroxide 2.00 Water 96.20 100.00
______________________________________
EXAMPLE 20
The example illustrates a gel suitable for treating hair containing
2-hydroxy-19-methyl-18-oxa-4-eicosenoic acid and
alpha-bisabolol.
______________________________________ Ingredient % w/w
______________________________________ Emulsifiers 20.00 Silicone
oil 20.00 Humectant 11.00 Lactic acid 5.00
2-Hydroxy-19-methyl-18-oxa-4- 1.50 eicosenoic acid Alpha-bisabolol
0.20 Triethanolamine 4.55 Fragrance 0.10 Water 37.65 100.00
______________________________________
EXAMPLE 21
The example illustrates a nail strenthener suitable for treating
dryness and brittleness, containing 2-hydroxy-4-tetracosenoic
acid.
______________________________________ Ingredient % w/w
______________________________________ Humectant 10.00 Mineral oil
10.00 2-Hydroxy-4-tetracosenoic acid 2.00 Potassium hydroxide 4.50
Water 73.50 100.00 ______________________________________
EXAMPLE 22
The example illustrates a lotion suitable for treatment of nails,
containing 2-hydroxy-4,9-decadienoic acid and beeswax.
______________________________________ Ingredient % w/w
______________________________________ Propane-1,2-diol 50.00
Ethanol 10.00 Beeswax 5.00 2-Hydroxy-4,9-decadienoic acid 3.00
Sodium chloride 3.00 Sodium hydroxide 4.25 Water 24.75 100.00
______________________________________
This lotion, having a pH value of 4.3, is made by the process, as
herein described, by homogenising the mixture of the
ingredients.
* * * * *